EP0868544A4 - Materiaux d'electrode destines a des elements electrochimiques, et leur procede de fabrication - Google Patents

Materiaux d'electrode destines a des elements electrochimiques, et leur procede de fabrication

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Publication number
EP0868544A4
EP0868544A4 EP96943655A EP96943655A EP0868544A4 EP 0868544 A4 EP0868544 A4 EP 0868544A4 EP 96943655 A EP96943655 A EP 96943655A EP 96943655 A EP96943655 A EP 96943655A EP 0868544 A4 EP0868544 A4 EP 0868544A4
Authority
EP
European Patent Office
Prior art keywords
carbon
electrode
monomers
acid
ray diffraction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96943655A
Other languages
German (de)
English (en)
Other versions
EP0868544A1 (fr
Inventor
Jinshan Zhang
Anaba A Anani
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Motorola Solutions Inc
Original Assignee
Motorola Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Motorola Inc filed Critical Motorola Inc
Publication of EP0868544A1 publication Critical patent/EP0868544A1/fr
Publication of EP0868544A4 publication Critical patent/EP0868544A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making

Definitions

  • This invention relates in general to the field of electrodes and electrode materials for electrochemical cells, and in addition, to methods of synthesizing said electrodes and electrode materials.
  • the main energy storage device used for portable electronics is the electrochemical battery cell, and less frequently, the electrochemical capacitor.
  • NiMH nickel metal hydride systems
  • Lithium ion batteries in general include a positive electrode or cathode fabricated of a transition metal oxide material, and a negative electrode or anode fabricated of an activated carbon material such as graphite or petroleum coke. New materials for both electrodes have been investigated intensely because of their high potential gravimetric energy density. To date, however, most of the attention has been focused on the transition metal oxide electrode.
  • Activated carbon materials are routinely prepared by using difunctional monomers as polymer precursors. Examples of such precursors include resins of furfuryl alcohol, phenol, formaldehyde, acetone-furfural, or furfural alcohol-phenol copolymer. These precursors are disclosed in, for example, U.S. Patent No.
  • FIG. 1 is a schematic representation of an electrochemical cell including an electrode fabricated of carbon electrode material, in accordance with the instant invention
  • FIG. 2 is a flowchart illustrating the steps for preparing a carbon electrode material, in accordance with the instant invention
  • FIG. 3 is a X-ray diffraction pattern of an amorphous carbon electrode material, in accordance with the instant invention
  • FIG. 4 is a X-ray diffraction pattern of a second amorphous carbon electrode material, in accordance with the instant invention
  • FIG. 5 is a X-ray diffraction pattern of a third amorphous carbon electrode material, in accordance with the instant invention.
  • FIG. 6 is a X-ray diffraction pattern of a fourth amorphous carbon electrode material, in accordance with the instant invention.
  • FIG. 7 is a X-ray diffraction pattern of a fifth amorphous carbon electrode material, in accordance with the instant invention.
  • FIG. 8 is a X-ray diffraction pattern of a sixth amorphous carbon electrode material, in accordance with the instant invention
  • FIG. 9 is a X-ray diffraction pattern of a seventh amorphous carbon electrode material, in accordance with the instant invention.
  • FIG. 10 is a X-ray diffraction pattern of an eighth amorphous carbon electrode material, in accordance with the instant invention.
  • FIG. 1 there is illustrated therein a schematic representation of an electrochemical cell 10 such as a battery or an electrochemical capacitor, and including an amorphous carbon or carbon- based electrode fabricated in accordance with the instant invention.
  • the electrochemical cell includes a positive electrode or cathode 20, a negative electrode or anode 30 and an electrolyte 40 disposed therebetween.
  • the cell negative electrode 30 is fabricated of a substantially amorphous carbon or carbon-based material such as that described in greater detail hereinbelow.
  • the positive electrode 20 of the cell 10 may be fabricated from a lithiated transition metal oxide such as are well known in the art.
  • the positive electrode material may be fabricated of a material such as that described in commonly assigned, co-pending patent application serial no. 08/464,440 filed June 5, 1995, in the name of Mao, et al, and entitled "Positive Electrode Materials for Rechargeable Electrochemical Cells and Method of Making Same", the disclosure of which is incorporated herein by reference.
  • the electrolyte 40 disposed between the electrodes may be a polymer electrolyte, comprising a polymeric support, having dispersed therein an electrolyte active species such as, for example, I CIO4 in propylene carbonate, or polyethylene oxide impregnated with a lithiated salt.
  • the electrolyte may be similar to that described in commonly assigned, co-pending Application Serial No. 08/518,732 filed August 24, 1995 to Oliver, the disclosure of which is incorporated herein by reference.
  • the electrolyte 40 may also act as a separator between the positive and negative electrodes.
  • the electrolyte may be aqueous, non-aqueous, solid state, gel, or some combination thereof.
  • a substantially amorphous carbon or carbon-based material for use as an electrode in an electrochemical device such as a battery, and a method for making said material.
  • the carbon-based materials are substantially amorphous, though may be partially or completely crystalline or include crystalline inclusions if desired, and may include an amount of one or more modifiers. The exact nature of the modifiers is dependent upon the specific application contemplated, as will be described below.
  • the instant invention uses one or more multifunctional organic monomers. More specifically, the multifunctional organic monomers are divided into two groups (Monomer A & Monomer B), at least one monomer being selected from each group.
  • the monomers have the general formulas of:
  • the instant invention contemplates fabricating the carbon materials from two or more than two multifunctional organic monomers, at least one of which is selected from each of the two groups described above.
  • one of the organic precursor monomers has at least three functional groups, which functional groups allow for crosslinking in the curing process. More particularly, first and second multifunctional organic monomers are cured or crosslinked in the presence of heat and /or a catalyst, as is described in greater detail hereinbelow. Following the curing process, the crosslinked multifunctional organic monomers are subjected to a solid state carbonization process described in greater detail hereinbelow. The result of the solid state carbonization process is the amorphous carbon electrode material.
  • Preferred compounds from monomer Group B include 1,3,5- benezenetricarbonyl trichloride, terephthaloyl chloride, dimethyl isophthalate, dimethyl terephthlate, isophthaloyl chloride, terephthalic acid, isophthalic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4- benzenetricarboxylic anhydride, 1,2,4,5-benzenetetracarboxylic acid, 1,2,4,5- benzenetetracarboxylic dianhydride, and combinations thereof.
  • Other multifunctional organic monomers which conform to the formulas described hereinabove may be employed equally advantageously, without departing from the spirit or scope hereof.
  • the carbon electrode materials resulting from the processing of the organic monomer precursors described hereinabove are characterized by X- ray diffraction patterns which individually show a (002) peak, the d- spacings of which (002) peaks (d ⁇ 02) are between 3.72 A to 4.20A. Further, the optimum peak ratio of the (002) peak to the (100) peak is between 1 and 5, and preferably between 2.25 and 2.75. Since the carbon materials are essentially amorphous in nature, the X-ray diffraction peaks are broader than in crystalline materials. This will be illustrated in the examples below.
  • the amorphous carbon electrode material may be formed with an acid present.
  • preferred acids include acids selected from the group consisting of acetic acid, boric acid, phosphoric acid, p- toluenesulfonic acid, 4-amino benzoic acid, trifluoroacetic acid, benzenesulfonic acid, and combinations thereof.
  • the acid may be present in amounts between 1 and 25% weight percent.
  • the carbon material may also include one or more modifiers incorporated into the carbon matrix.
  • the modifiers may be selected from the group consisting of lithium alloying elements such as Sn, Si, Al, and others known in the art, and combinations thereof, and electrode performance enhancing elements such as B, N, Ti, V, and combinations thereof.
  • the multifunctional organic monomers are heated, along with the acid catalyst, in an inert environment.
  • Preferred inert gas environments include, for example, nitrogen, argon, and helium.
  • the materials are heated at temperatures sufficient to induce a solid state carbonization of the multifunctional monomers. This process is similar in nature to a sublimation process, and occurs at temperatures of less than about 1200°C, and preferably about 1000°C.
  • the amorphous carbon electrode material is the pyrolytic by-product of the multifunctional organic monomers.
  • the multifunctional monomers are cured or polymerized at lower temperatures. Once polymerized, the multifunctional monomers form a cured, crosslinked polymer which subsequently carbonizes at higher temperatures to form the carbon electrode material.
  • the carbonization process refers to the fact that the cross-linked organic precursors decompose, evolving compounds including carbon-oxygen, carbon-hydrogen, hydrogen-oxygen, nitrogen- hydrogen, and other similar compounds. The remaining carbon atoms condense into planar structures terminating predominantly with edge hydrogen atoms, the amount of hydrogen atoms.
  • the fabrication process may be understood from the following:
  • Multifunctional Monomers wherein Monomer A and Monomer B are selected from the groups described above.
  • the cross-linked polymer resulting from the curing process decomposes and forms carbon-carbon bonds between the phenyl rings of the starting monomers.
  • the temperature increases up to, for example, 500°-700°C
  • the six carbon phenyl rings start to break and form a layered carbon network.
  • the formation of hyperbranched carbon polymers in the first stage of the process results in moving the monomer molecules physically closer to one another, thus facilitating carbonization in the second step of the process. This also accounts, at least partially, for improved yields as compared to the prior art.
  • the first step illustrated in FIG. 2 is shown in box 102, and comprises the step of selecting appropriate multifunctional organic monomers from each group. Thereafter, as illustrated in box 103, the two or more organic monomers are cured or cross-linked by heating. Then, as illustrated in box 104, is the step of selecting the treatment temperature ranges for the solid state carbonization process for the selected monomers. More particularly, the yield of the amorphous carbon material from a particular multifunctional monomer will depend in part on the thermal regime to which the monomer is subjected. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) each provide means by which to determine the processing temperature regime. The results have generally indicated that the solid state carbonization process should be a two temperature, one-step heating process.
  • TGA Thermogravimetric analysis
  • DSC differential scanning calorimetry
  • TGA & DSC indicate the temperature at which condensation and reduction of the multifunctional monomers occur.
  • the next step in the fabrication process of flow chart 100 is illustrated in box 106, and comprises the step of mixing the multifunctional organic monomers with an acid selected from the group of acids described above.
  • the materials should be mixed thoroughly, and further may be dried, as in a drying oven, prior to subjecting the mixture to the solid state carbonization process.
  • the organic monomers may be mixed with or without the acid, in the presence of an organic solvent such as tetrahydrofuran, acetonitrile, methyl sulfoxide, and combinations thereof.
  • step 108 is the solid state carbonization process 108, which may comprise a multi-step heating regime.
  • step 108 actually comprises four steps illustrated by boxes 110, 112, 114, and 116.
  • Each step in the carbonization process will depend upon the DSC and TGA testing described above.
  • the step illustrated by box 110 comprises the step of heating the dried monomers and optional acid to a first temperature at a predetermined rate of X°C/minute. Once the desired temperature is reached, the mixture is held at that temperature for a predetermined time period, as illustrated in box 112. Thereafter, the material is heated to a second, typically higher temperature, at a rate of X°C/minute, as illustrated in box 114. Once the second desired temperature is reached, the mixture is held at that temperature for a predetermined time period, as illustrated in box 116. After solid state carbonization is completed, the resulting carbon electrode material is cooled slowly as illustrated in box 118.
  • FIG. 3 is an X-ray diffraction pattern for the material of this example, and shows a broad (002) peak centered at 4.03A.
  • FIG. 3 also shows an intensity peak ratio of of 2.48.
  • the reversible lithium intercalation capacity of the material was 520 mAh/g.
  • FIG. 4 is an X-ray diffraction pattern for the carbon material of this example, and shows a broad (002) peak in the range of 4.06 to 3.90A, and centered at 4.0 ⁇ A.
  • FIG. 4 also shows an intensity peak ratio of of 2.25.
  • the reversible lithium intercalation capacity of the material was 480 mAh/g.
  • FIG. 5 is an X-ray diffraction pattern for the material of this example, and shows a broad (002) peak centered at at 3.95A.
  • FIG. 5 also shows an instensity peak ratio of
  • FIG. 6 is an X-ray diffraction pattern for the material of this example, and shows a broad (002) peak centered at at
  • FIG. 6 also shows an intensity peak ratio of of 2.65.
  • the reversible lithium intercalation capacity of the material was 470 mAh/g.
  • Terephthaloyl chloride (24.04 g) and pentaerythritol powder (8.00g) were mixed in a ball mill.
  • the mixture was placed in a ceramic crucible and cured at 100°C for 12 hours.
  • the cured polymer was then carbonized according to the following heating program in an inert gas atmosphere of argon: (1) 100°C to 260 °C at l°C/min; (2) hold at 260°C for 6 hours; (3) from 260°C to 1000°C at 10°C/min; (4) hold at 1000 °C for 6 hours. 5.01 g of carbon electrode material was collected.
  • FIG. 7 is an X-ray diffraction pattern for the material of this example, and shows a broad (002) peak centered at at 3.95A.
  • FIG. 7 also shows an intensity peak ratio of of 2.25.
  • the reversible lithium intercalation capacity of the material was 430 mAh/g.
  • Terephthaloyl chloride (24.04 g) and pentaerythritol powder (8.00g) were mixed in a ball mill.
  • the mixture was placed in a ceramic crucible and cured at 100°C for 12 hours.
  • the cured polymer was then carbonized according to the following heating program in an inert gas atmosphere of argon: (1) 100°C to 260 °C at l°C/min; (2) hold at 260°C for 6 hours; (3) from 260°C to 1200°C at 10°C/min; (4) hold at 1200 °C for 6 hours. 4.85 g of carbon electrode material was collected.
  • FIG. 8 is an X-ray diffraction pattern for the material of this example, and shows a (002) peak in the range of 4.92 to 3.79 A, and centered at at 3.95A.
  • FIG. 8 also shows an I ( 002) intensity peak ratio of of 2.25.
  • the reversible lithium intercalation capacity of the material was 420 mAh/g.
  • Dimethyl isophthalate (19.4 g), pentaerythritol powder (6.80g), and p- toluenesulfonic acid (1.94 g) were mixed and placed in a ceramic crucible. After heating at 80°C for about 30 minutes, the mixture became a viscous liquid. The liquid was subsequently cured at 130°C for 12 hours. The cured polymer was carbonized according to the following heating program in an inert gas atmosphere of argon: (1) 130°C to 600 °C at 0.5°C/min; (2) from 600°C to 1100°C at 10°C/min; (4) hold at 1100 °C for 1 hour. 4.05 g of carbon electrode material was collected.
  • FIG. 9 is an X-ray diffraction for the material of this example, and shows a broad (002) peak centered at 3.95A.
  • FIG. 9 also shows an intensity peak ratio of of 2.43.
  • the reversible lithium intercalation capacity of the material was 340 mAh/g.
  • Dimethyl terephthalate (19.4 g), pentaerythritol powder (6.80g), and p- toluenesulfonic acid (1.94 g) were mixed and placed in a ceramic crucible. After heating at 80°C for about 30 minutes, the mixture became a viscous liquid. The liquid was subsequently cured at 130°C for 12 hours. The cured polymer was carbonized according to the following heating program in an inert gas atmosphere of argon: (1) 130°C to 600 °C at 0.5°C/min; (2) from 600°C to 1100°C at 10°C/min; (4) hold at 1100 °C for 1 hour. 4.05 g of carbon was collected.
  • FIG. 10 is an X-ray diffraction pattern for the material of this example, and shows a (002) peak centered at 3.83A.
  • FIG. 10 also shows an intensity peak ratio of of 2.38.
  • the reversible lithium intercalation capacity of the material was 330 mAh/g.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

On décrit un procédé permettant de préparer un matériau à base de carbone, utilisable en guise d'électrode, telle l'anode (30) d'un élément électrochimique (10). On fabrique ce carbone à chaud à partir de plusieurs monomères organiques multi-fonctionnels sélectionnés dans deux groupes distincts. Les électrodes ainsi fabriquées peuvent être intégrées à des éléments électrochimiques (10) sous forme d'anodes (20).
EP96943655A 1995-12-20 1996-12-12 Materiaux d'electrode destines a des elements electrochimiques, et leur procede de fabrication Withdrawn EP0868544A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US08/575,653 US5647963A (en) 1995-12-20 1995-12-20 Electrode materials for electrochemical cells and method of making same
US575653 1995-12-20
PCT/US1996/019566 WO1997022734A1 (fr) 1995-12-20 1996-12-12 Materiaux d'electrode destines a des elements electrochimiques, et leur procede de fabrication

Publications (2)

Publication Number Publication Date
EP0868544A1 EP0868544A1 (fr) 1998-10-07
EP0868544A4 true EP0868544A4 (fr) 1999-09-15

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP96943655A Withdrawn EP0868544A4 (fr) 1995-12-20 1996-12-12 Materiaux d'electrode destines a des elements electrochimiques, et leur procede de fabrication

Country Status (4)

Country Link
US (3) US5647963A (fr)
EP (1) EP0868544A4 (fr)
JP (1) JP2000502491A (fr)
WO (1) WO1997022734A1 (fr)

Families Citing this family (10)

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Publication number Priority date Publication date Assignee Title
JP3724099B2 (ja) * 1996-02-22 2005-12-07 ソニー株式会社 非水電解液二次電池用炭素質負極材料の製造方法
KR100269923B1 (ko) * 1998-03-10 2000-10-16 김순택 리튬 계열 이차 전지의 음극용 활물질의 제조 방법
JP2000077273A (ja) * 1998-09-03 2000-03-14 Ngk Insulators Ltd 電気二重層コンデンサ及びその製造方法
US6280697B1 (en) * 1999-03-01 2001-08-28 The University Of North Carolina-Chapel Hill Nanotube-based high energy material and method
FR2889917A1 (fr) * 2005-09-01 2007-03-02 Ela Medical Soc Par Actions Si Equipement de telemetrie pour communiquer avec un dispositif actif implante dans une region du thorax d'un patient
US7850848B2 (en) * 2006-09-18 2010-12-14 Limcaco Christopher A Apparatus and process for biological wastewater treatment
JP5534000B2 (ja) * 2010-02-18 2014-06-25 株式会社村田製作所 全固体二次電池用電極活物質および全固体二次電池
CN107430946B (zh) * 2015-03-31 2020-05-08 株式会社大阪曹达 电化学电容器
CN110783629B (zh) * 2019-11-19 2021-01-15 广州天赐高新材料股份有限公司 一种锂二次电池用电解液和锂二次电池
US11606889B2 (en) * 2020-03-31 2023-03-14 Mazda Motor Corporation Carbon material filler for electromagnetic shield, electromagnetic shield material, and carbon-material-containing molded body for electromagnetic shield

Citations (2)

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Publication number Priority date Publication date Assignee Title
EP0486950A1 (fr) * 1990-11-17 1992-05-27 Sony Corporation Batterie secondaire à électrolyte non aqueux
EP0565273A1 (fr) * 1992-04-09 1993-10-13 Sanyo Electric Co., Limited. Batterie secondaire et procédé pour sa fabrication

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0418514B1 (fr) * 1989-07-29 1994-05-18 Sony Corporation Matériau carboné et cellule électrochimique non-aqueuse utilisant ce matériau
JP3054473B2 (ja) * 1991-10-08 2000-06-19 三洋電機株式会社 二次電池
EP0541889B1 (fr) * 1991-11-12 1998-09-09 Sanyo Electric Co., Limited. Batterie secondaire au lithium
US5536597A (en) * 1993-12-17 1996-07-16 Mitsubishi Gas Chemical Company Lithium secondary battery employing a non-aqueous electrolyte

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
EP0486950A1 (fr) * 1990-11-17 1992-05-27 Sony Corporation Batterie secondaire à électrolyte non aqueux
EP0565273A1 (fr) * 1992-04-09 1993-10-13 Sanyo Electric Co., Limited. Batterie secondaire et procédé pour sa fabrication

Non-Patent Citations (1)

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Title
See also references of WO9722734A1 *

Also Published As

Publication number Publication date
JP2000502491A (ja) 2000-02-29
US5647963A (en) 1997-07-15
EP0868544A1 (fr) 1998-10-07
WO1997022734A1 (fr) 1997-06-26
US5677085A (en) 1997-10-14
US5688483A (en) 1997-11-18

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